CN103328475A - Compound having pyridoindole ring structure and substituted bipyridyl group, and organic electroluminescent element - Google Patents
Compound having pyridoindole ring structure and substituted bipyridyl group, and organic electroluminescent element Download PDFInfo
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- CN103328475A CN103328475A CN2012800057761A CN201280005776A CN103328475A CN 103328475 A CN103328475 A CN 103328475A CN 2012800057761 A CN2012800057761 A CN 2012800057761A CN 201280005776 A CN201280005776 A CN 201280005776A CN 103328475 A CN103328475 A CN 103328475A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 88
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- IVCGJOSPVGENCT-UHFFFAOYSA-N 1h-pyrrolo[2,3-f]quinoline Chemical group N1=CC=CC2=C(NC=C3)C3=CC=C21 IVCGJOSPVGENCT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 66
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 25
- 239000012044 organic layer Substances 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 127
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 22
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 230000000903 blocking effect Effects 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005401 electroluminescence Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000002347 injection Methods 0.000 abstract description 18
- 239000007924 injection Substances 0.000 abstract description 18
- 150000002894 organic compounds Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract 1
- -1 phenylene compound Chemical class 0.000 description 28
- 238000000034 method Methods 0.000 description 22
- 239000002585 base Substances 0.000 description 19
- 230000004888 barrier function Effects 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 16
- 238000010276 construction Methods 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- NTEHSMCNSXIYEW-UHFFFAOYSA-N 5-phenylpyrido[4,3-b]indole Chemical class C1=CC=CC=C1N1C2=CC=NC=C2C2=CC=CC=C21 NTEHSMCNSXIYEW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 3
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- 125000001725 pyrenyl group Chemical group 0.000 description 3
- 150000004322 quinolinols Chemical class 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 2
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- CZZLHOWUECFBMS-UHFFFAOYSA-N 8-bromo-5-phenylpyrido[4,3-b]indole Chemical class C12=CC=NC=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 CZZLHOWUECFBMS-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002475 indoles Chemical class 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000007978 oxazole derivatives Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 150000003921 pyrrolotriazines Chemical class 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QJZJIWYDCCBNTH-UHFFFAOYSA-N 9-[4-(9H-fluoren-1-yl)phenyl]carbazole Chemical class C1=CC=CC=2C3=CC=CC=C3N(C1=2)C1=CC=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC1=2 QJZJIWYDCCBNTH-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical class C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- IYRHBDVSMINOTQ-UHFFFAOYSA-N aniline;ethene Chemical compound C=C.NC1=CC=CC=C1 IYRHBDVSMINOTQ-UHFFFAOYSA-N 0.000 description 1
- MWPLVEDNUUSJAV-LSMJWXKXSA-N anthracene Chemical group [13CH]1=[13CH][13CH]=[13CH][13C]2=CC3=CC=CC=C3C=[13C]21 MWPLVEDNUUSJAV-LSMJWXKXSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VVUBWCWVDFCEOP-UHFFFAOYSA-N benzene;styrene Chemical class C1=CC=CC=C1.C=CC1=CC=CC=C1 VVUBWCWVDFCEOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical class C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 1
- DETFWTCLAIIJRZ-UHFFFAOYSA-N triphenyl-(4-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DETFWTCLAIIJRZ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
Abstract
[Problem] To provide an organic compound that, as a material for a highly efficient and highly durable organic electroluminescent element, has the superior characteristic of high stability in a thin-film state, has hole-blocking ability, and has superior electron injection/transport performance, and to provide a highly efficient and highly durable organic electroluminescent element using the compound. [Solution] In the compound, the substituted bipyridyl group represented by general formula (1) and a pyridoindole ring structure are coupled with a phenylene group therebetween. The organic electroluminescent element, which has a pair of electrodes and at least one organic layer sandwiched between the pair of electrodes, is characterized by the compound being used as a constituent material of at least one organic layer.
Description
Technical field
The present invention relates to be suitable for organic electroluminescence device (below, referred to as organic EL device) compound and used the organic EL device of this compound, described organic EL device is the selfluminous element that is useful on the various display unit, specifically, relating to substituted bipyridyl and pyrido indole ring structure is situated between by the phenylene compound that is formed by connecting and the organic EL device that has used this compound.
Background technology
Organic EL device is the self-luminosity device, thus bright and visual more excellent than liquid crystal device, can show clearly, so it has been carried out positive research.
In 1987, the C.W.Tang of Eastman Kodak Company etc. form various functional distributions by exploitation to each material stepped construction device, thus will use the organic EL device of organic materials to drop into practical application.Their fluor by can transmission electronic and organism that can transporting holes carry out stacked, thereby make both charge injections make it luminous in the layer of fluor, obtain 1000cd/m thus under the voltage below the 10V
2Above high brightness (for example with reference to patent documentation 1 and patent documentation 2).
Up to now, many improvement have been carried out for the practical of organic EL device, with the further sectionalization of various effects, by be disposed with the electroluminescent device of anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode at substrate, high-level efficiency and weather resistance (for example with reference to non-patent literature 1) have been realized.
In addition, in order further to improve luminous efficiency, attempt utilizing triplet exciton, studied the utilization (for example with reference to non-patent literature 2) of phosphorescence twinkler.
Luminescent layer also can be made by doping fluorescent body in the compound of the charge-transporting that is commonly called material of main part, phosphorescence twinkler.In non-patent literature 1 described above and the non-patent literature 2 record like that, the selection of the organic materials in the organic EL device makes a big impact to various characteristicses such as the efficient of this device, weather resistance.
In organic EL device, from the electric charge of two electrode injections luminescent layer again in conjunction with and realize luminous, yet, because the travelling speed in hole is higher than the travelling speed of electronics, can produce thus the problem of being passed the Efficiency Decreasing that luminescent layer causes by the part hole.Therefore the fast electron transport material of travelling speed that needs a kind of electronics.
Representational luminescent material namely three (oxine) aluminium (below, referred to as Alq
3) usually also use as electron transport material, but because electronic migration speed is slow and work function is 5.6eV, so the hole barrier performance does not claim fully.
Pass luminescent layer, improve electric charge method of the probability of combination again in luminescent layer as a part that prevents the hole, the method for inserting hole blocking layer is arranged.As hole barrier materials, triazole derivative has been proposed up to now (for example, with reference to patent documentation 3), bathocuproine (below, referred to as BCP), the mixed ligand complex of aluminium [two (2-methyl-oxine base)-4-phenylphenol aluminium (III) (below, referred to as BAlq)] (for example, with reference to non-patent literature 2) etc.
On the other hand, as the electron transport material of hole barrier excellence, 3-(4-xenyl)-4-phenyl-5-(4-tert-butyl-phenyl)-1,2 has been proposed, the 4-triazole (below, referred to as TAZ) (for example, with reference to patent documentation 3).
Because TAZ has the work function up to 6.6eV, and the hole barrier ability is high, thereby used as the hole blocking layer of electron-transporting, and be layered in by the fluorescence radiation layer of the making such as vacuum evaporation, coating or the cathode side of phosphorescence luminescent layer, help to increase the efficient (for example, with reference to non-patent literature 3) of organic EL device.
Yet TAZ has the low larger problem of electron-transporting, need to make up to make organic EL device (for example, with reference to non-patent literature 4) with the higher electron transport material of electron-transporting.
In addition, although the BCP work function is also high up to 6.7eV and hole barrier ability, because second-order transition temperature (Tg) is low to moderate 83 ℃, so the stability of film shortcoming, it does not play a role fully as hole blocking layer is talkative.
The function of above-mentioned materials or membrane stability deficiency or blocking hole is insufficient.In order to improve the device property of organic EL device, need that the injection/transmission performance of electronics and hole barrier ability are excellent, the stable high organic compound under the filminess.
As the compound of having improved these, proposed to have the compound (for example, with reference to patent documentation 4) of anthracene nucleus structure and benzoglyoxaline ring structure.
Yet, for the device that has used these compounds in electron injecting layer and/or the electron transfer layer, although its luminous efficiency etc. is improved, can't say fully, require low driving voltage, further high-luminous-efficiency, especially high current efficiency.
Existing patented technology
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-48656 communique
Patent documentation 2: No. 3194657 communique of Japan's special permission
Patent documentation 3: No. 2734341 communique of Japan's special permission
Patent documentation 4:WO2003/060956 communique
Non-patent literature
Non-patent literature 1: the 9th pre-original text collection of seminar of Applied Physics association (ying can give the original text collection with the 9th time Talk Xi of physical society) 55～61 pages (2001)
Non-patent literature 2: the 9th pre-original text collection of seminar of Applied Physics association (ying can give the original text collection with the 9th time Talk Xi of physical society) 23～31 pages (2001)
3: the 50 times applied physics of non-patent literature concern that the 28p-A-6 of associating oratorical contest gives a lecture pre-original text collection (the 50th time ying drilled can 28p-A-6 Talk to drill with Wu Li Off Department Even He Talk and given the original text collection) 1413 pages (2003)
Non-patent literature 4: applied physics can organic molecular bioelectronics branch can will (ying has Machine molecule バ イ オ エ レ Network ト ロ ニ Network ス branch with physics can Chi) No. 1,11 volumes 13～19 pages (2000)
Non-patent literature 5:J.Chem.Soc., Perkin Trans.1,1505 (1999)
Non-patent literature 6:J.Org.Chem., 60,7508 (1995)
Non-patent literature 7:Synth.Commun., 11,513 (1981)
Non-patent literature 8:Synthesis, 1 (1976)
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of organic compound, it is as the material of the organic EL device that is used for high-level efficiency, high-durability, has excellent characteristic, be that electronic injection/transmission performance is excellent, has the hole barrier ability, stable high under filminess also provides the organic EL device with high-level efficiency, high-durability that has used this compound.
The physical property that the organic compound that will provide as the present invention should possess, can list: the injection properties of (1) electronics is good, and the travelling speed of (2) electronics is fast, and (3) hole barrier ability is excellent, (4) filminess is stable, (5) excellent heat resistance.In addition, the physical property that the organic EL device that will provide as the present invention should possess can list: (1) luminous efficiency and electrical efficiency are high, and (2) luminous starting voltage is low, and (3) practical driving voltage is low.
For the scheme of dealing with problems
Therefore, the inventor etc. in order to achieve the above object, ability, pyrido indole ring structure that the nitrogen-atoms that is conceived to the pyridine ring of electron affinity has with metal-complexing have excellent heat resistance of high electron transport ability, pyridine ring and pyrido indole ring structure etc., design and chemosynthesis substituted bipyridyl and the pyrido indole ring structure compound that is situated between and is formed by connecting by phenylene, use this compound to manufacture experimently various organic EL devices, device is carried out deep evaluating characteristics, and the result has finished the present invention.
That is, the present invention is compound shown in the general formula (1), that substituted bipyridyl and pyrido indole ring structure are situated between and are formed by connecting by phenylene.
(in the formula, Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms.Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17)
In addition, the present invention is the compound that bipyridyl shown in the following general formula (1 '), substituted and pyrido indole ring structure are situated between and are formed by connecting by phenylene.
(in the formula, Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms.Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17)
In addition, the present invention is compound shown in the following general formula (1 "), that substituted bipyridyl and pyrido indole ring structure are situated between and are formed by connecting by phenylene.
(in the formula, Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms.Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17)
In addition, the present invention is a kind of organic EL device, it has at least one deck organic layer of pair of electrodes and clamping therebetween, wherein, at least one deck of aforementioned organic layer comprises compound shown in aforementioned formula (1), (1 ') or (1 "), that substituted bipyridyl and pyrido indole ring structure are situated between and are formed by connecting by phenylene.
As the Ar in general formula (1), (1 ') or (1 ")
1, Ar
2Shown, " replace or unsubstituted aromatic hydrocarbyl ", " replace or unsubstituted aromatic heterocycle " or " aromatic hydrocarbyl " in " replacing or unsubstituted condensed polycyclc aromatic base ", " aromatic heterocycle " or " condensed polycyclc aromatic base ", particularly, can list phenyl, xenyl, terphenyl, the tetrad phenyl, styryl, naphthyl, anthryl, acenaphthenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, pyridyl, triazinyl, pyrimidyl, furyl, pyrryl, thienyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indyl, carbazyl benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl-, pyrazolyl, dibenzofuran group, the dibenzothiophene base, naphthyridinyl, the phenanthroline base, the group of acridyl and so on.
As the Ar in general formula (1), (1 ') or (1 ")
1, Ar
2Shown, " substituted aromatic alkyl ", " substituting group " in " substituted aromatic heterocyclic radical " or " substituted fused Ppolynuclear aromatic base ", particularly, can list D atom, fluorine atom, the chlorine atom, cyano group, trifluoromethyl, hydroxyl, nitro, the alkyl of the straight chain shape of carbonatoms 1～6 or a chain, cyclopentyl, cyclohexyl, the straight chain shape of carbonatoms 1～6 or a chain alkoxyl group, by the dialkyl amido of the alkyl replacement of the straight chain shape of carbonatoms 1～6 or a chain, phenyl, naphthyl, anthryl, fluorenyl, styryl, pyridyl, the pyrido indyl, quinolyl, the group of benzothiazolyl and so on, these substituting groups can further be substituted.
As the Ar in general formula (1), (1 ') or (1 ")
1, preferred " replacing or unsubstituted aromatic hydrocarbyl " or " replacing or unsubstituted condensed polycyclc aromatic base ", particularly preferably replace or unsubstituted, phenyl, naphthyl, anthryl or fluorenyl.
As the Ar in general formula (1), (1 ') or (1 ")
2, preferred " replacing or unsubstituted aromatic hydrocarbyl ", particularly preferably replace or unsubstituted phenyl.
As the R in general formula (1), (1 ') or (1 ")
1～R
17Shown, " replace or unsubstituted aromatic hydrocarbyl ", " replace or unsubstituted aromatic heterocycle " or " aromatic hydrocarbyl " in " replacing or unsubstituted condensed polycyclc aromatic base ", " aromatic heterocycle " or " condensed polycyclc aromatic base ", particularly, can list phenyl, xenyl, terphenyl, the tetrad phenyl, styryl, naphthyl, anthryl, acenaphthenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, pyridyl, triazinyl, pyrimidyl, furyl, pyrryl, thienyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indyl, carbazyl benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl-, pyrazolyl, dibenzofuran group, the dibenzothiophene base, naphthyridinyl, the phenanthroline base, the group of acridyl and so on.
Herein, as R
1～R
4Shown, " replacing or unsubstituted aromatic heterocycle ", preferably replace or unsubstituted pyridyl, can expect the raising of Electron Injection Characteristics.
As the R in general formula (1), (1 ') or (1 ")
1～R
17" substituting group " in shown, " substituted aromatic alkyl ", " the substituted aromatic heterocyclic radical " or " substituted fused Ppolynuclear aromatic base ", particularly, can list the group of the alkyl, phenyl, xenyl, terphenyl, tetrad phenyl, styryl, naphthyl, fluorenyl, phenanthryl, indenyl, pyrenyl, pyrido indyl and so on of the straight chain shape of D atom, fluorine atom, chlorine atom, trifluoromethyl, carbonatoms 1～6 or chain, these substituting groups can further be substituted.
As the R in general formula (1), (1 ') or (1 ")
1～R
17Shown, " alkyl of the straight chain shape of carbonatoms 1～6 or a chain ", particularly, can list the group of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl and so on.
As shown in general formula of the present invention (1), (1 ') or (1 "), substituted bipyridyl and the pyrido indole ring structure bipyridyl in the compound that is formed by connecting by phenylene that is situated between; from stable on heating viewpoint; preferred [2,3 '] bipyridyl.
Shown in general formula of the present invention (1), (1 ') or (1 "), substituted bipyridyl and the pyrido indole ring structure compound that is formed by connecting by phenylene that is situated between is novel cpd; the travelling speed of comparing electronics with electron transport material in the past is fast, have excellent hole barrier ability, and filminess is stable.
Shown in general formula of the present invention (1), (1 ') or (1 "), substituted bipyridyl and pyrido indole ring structure are situated between the compound that is formed by connecting by phenylene can be as the electron injecting layer of organic EL device and/or the constituent material of electron transfer layer.Injection by using electronics/travelling speed is than in the past the higher material of material, and have following effect: the efficient from electron transfer layer to the luminescent layer transmission electronic improves, and luminous efficiency improves, and driving voltage reduces, and the weather resistance of organic EL device improves.
Shown in general formula of the present invention (1), (1 ') or (1 "), substituted bipyridyl and pyrido indole ring structure are situated between the compound that is formed by connecting by phenylene also can be as the constituent material of the hole blocking layer of organic EL device.Has excellent hole barrier ability and electron-transporting is more excellent than material in the past and the stable high material of filminess by use, has following effect: have high-luminous-efficiency, and driving voltage reduces, electric current patience improves, and the maximum luminousing brightness of organic EL device improves.
Shown in general formula of the present invention (1), (1 ') or (1 "), substituted bipyridyl and pyrido indole ring structure are situated between the compound that is formed by connecting by phenylene also can be as the constituent material of the luminescent layer of organic EL device.Electron-transporting is compared in use with material in the past excellent and with the material of the present invention of the gap length material of main part as luminescent layer, and the fluorescent illuminant that this material of main part is supported be known as hotchpotch, phosphorescence twinkler and use as luminescent layer, have following effect: can realize the organic EL device that driving voltage reduces, luminous efficiency is improved.
The compound that organic EL device of the present invention uses substituted bipyridyl and pyrido indole ring structure to be situated between and to be formed by connecting by phenylene, described compound is compared electronics with electron transport material in the past migration hole barrier ability and filminess fast, that have excellence is stable, therefore, become and to realize high-level efficiency, high-durability.
The effect of invention
The be situated between compound that is formed by connecting by phenylene of substituted bipyridyl of the present invention and pyrido indole ring structure is useful as the constituent material of electron injecting layer, electron transfer layer, hole blocking layer or the luminescent layer of organic EL device, its hole barrier ability is excellent, and filminess is stable.Luminous efficiency and the electrical efficiency of organic EL device of the present invention are high, can reduce thus the practical driving voltage of device.Can reduce luminous starting voltage, the improvement weather resistance.
Description of drawings
Fig. 1 is the compound (compound 2) of the embodiment of the invention 1
1The H-NMR spectrogram.
Fig. 2 is the compound (compound 8) of the embodiment of the invention 2
1The H-NMR spectrogram.
Fig. 3 is the figure that the El element of expression embodiment 5～6, comparative example 1 consists of.
Embodiment
The compound that substituted bipyridyl of the present invention and pyrido indole ring structure Jie are formed by connecting by phenylene is novel cpd, and these compounds can synthesize by for example following mode.At first, make corresponding halogeno-benzene amido pyridine carry out cyclization by palladium catalyst and (for example synthesize corresponding pyrido enatiomers of indole ring derivatives, with reference to non-patent literature 5), make the halogenide of itself and various aromatic hydrocarbon compound, condensed polycyclc aromatic compound or aromatic heterocyclic compounds carry out the condensation reactions such as Ullmann reaction, Buchward-Hartwig reaction, thus can synthesize corresponding 5 by aryl substiuted pyridoindole derivatives and processes.Should be corresponding 5 utilized N-bromo-succinimide etc. to carry out bromination by aryl substiuted pyridoindole derivatives and processes, synthesize thus corresponding bromination body, then, should be corresponding the bromination body utilize two (pinacol) two boron etc. to carry out acid esterification, synthetic corresponding boric acid ester body (for example thus, with reference to non-patent literature 6), and then, make this corresponding boric acid ester body carry out the cross-coupling reaction such as Suzuki coupling with the various halogeno-benzenes with bipyridyl (for example, with reference to non-patent literature 7), can synthesize thus the compound that substituted bipyridyl and pyrido indole ring structure are situated between and are formed by connecting by phenylene.Having the various halo phenylenes of bipyridyl herein, can be by making corresponding aldehyde and acetylpyridine condensation, further coming synthetic (for example, with reference to non-patent literature 8) with the reaction of corresponding pyridine iodide in the presence of alkali.
Substituted bipyridyl shown in general formula of the present invention (1), (1 ') or (1 ") and pyrido indole ring structure are situated between among the compound that is formed by connecting by phenylene; the object lesson of preferred compound is as follows, but the present invention is not subject to these compounds.
The purifying of these compounds is undertaken by the purifying that utilizes column chromatography, the adsorption and purification that utilizes silica gel, gac, atlapulgite etc., the recrystallization that utilizes solvent or crystallization etc.The evaluation of compound is analyzed to carry out by NMR.As physics value, carry out the mensuration of fusing point, second-order transition temperature (Tg) and work function.Fusing point is the index of evaporation, and second-order transition temperature (Tg) is the index of the stability of filminess, and work function is the index of hole barrier ability.
Fusing point and second-order transition temperature (Tg) use powder, and (Bruker AXS K.K. system DSC3100S) is measured by the highly sensitive differential scanning calorimeter.
In addition, about work function, make the film of 100nm at ito substrate, use photoelectron spectrum device in the atmosphere (Riken Keiki Co., Ltd. makes, the AC-3 type) to measure.
As the structure of organic EL device of the present invention, can list the structure that on substrate, is formed by anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode successively; In addition, the structure that between anode and hole transmission layer, has hole injection layer; The structure that between electron transfer layer and negative electrode, has electron injecting layer; The structure that between luminescent layer and hole transmission layer, has electronic barrier layer.In these multilayered structures, which floor organic layer can be omitted, for example the structure that has successively anode, hole transmission layer, luminescent layer, electron transfer layer, negative electrode on the substrate can be formed in.
Aforementioned light emission layer, aforementioned hole transmission layer, aforementioned electronic transport layer can be respectively and be laminated with two-layer above structure.
As the anode of organic EL device of the present invention, can use the large electrode materials of work function of ITO, gold and so on.Hole injection layer as organic EL device of the present invention, except the porphyrin compound take copper phthalocyanine as representative, can use have 3 above triphenylamine structures by singly-bound in the triphenylamine derivative, molecule of starlike (Starburst) or do not contain the triphenylamine tripolymer of novel arylamine compound etc. of the structure that heteroatomic divalent group connects and the tetramer, such as the receptor type heterogeneous ring compound of six cyano group azepine benzophenanthrenes and so on or the macromolecular material of application type.Except vapour deposition method, these materials can pass through the known method such as method of spin coating, ink jet method and form film.
Hole transmission layer as organic EL device of the present invention, can use N, N '-phenylbenzene-N, N '-two (tolyl) p-diaminodiphenyl (below, referred to as TPD), N, N '-phenylbenzene-N, N '-two (Alpha-Naphthyl) p-diaminodiphenyl (below, referred to as NPD), N, N, N ', the N '-benzidine derivatives, 1 such as tetrad phenyl p-diaminodiphenyl, two [(two-4-toluino) phenyl] hexanaphthenes of 1-(below, referred to as TAPC), various triphenylamine tripolymer and the tetramer etc.They are film forming separately, also can be with film forming after other material mixing use as individual layer, can also for the stepped construction between the layer of independent film forming, mix between the layer of film forming stepped construction or separately film forming layer with mixes rear film forming layer stepped construction.In addition, as the injection/transport layer in hole, can use the macromolecular material of the application type such as poly-(3,4-ethylene dioxythiophene) (below, referred to as PEDOT)/poly-(styrene sulfonate) (below, referred to as PSS).Except vapour deposition method, these materials can pass through the known method such as method of spin coating, ink jet method and form film.
In addition, in hole injection layer or hole transmission layer, can use has mixed for the further P of normally used material in this layer has macromolecular compound of TPD structure etc. in the product, its part-structure of tribromo phenyl chlordene ammonium antimonate etc.
Electronic barrier layer as organic EL device of the present invention, can use 4,4 '; 4 "-three (N-carbazyl) triphenylamine (below, referred to as TCTA), 9, two [4-(carbazole-9-yl) phenyl] fluorenes, 1 of 9-, two (carbazole-9-yl) benzene of 3-(below, referred to as mCP), 2, the carbazole derivative such as 2-two (4-carbazole-9-base phenyl) diamantane (below, referred to as Ad-Cz); Take 9-[4-(carbazole-9-yl) phenyl]-9-[4-(triphenyl silyl) phenyl]-the 9H-fluorenes has the compound of electronic blocking effect as compound with triphenyl silyl and triarylamine structure of representative etc.They are film forming separately, also can be with film forming after other material mixing use as individual layer, can also for the stepped construction between the layer of independent film forming, mix between the layer of film forming stepped construction or separately film forming layer with mixes rear film forming layer stepped construction.Except vapour deposition method, these materials can pass through the known method such as method of spin coating, ink jet method and form film.
As the luminescent layer of organic EL device of the present invention, except the compound that uses substituted bipyridyl of the present invention and pyrido indole ring structure to be situated between to be formed by connecting by phenylene with A1q
3Beyond the metal complex of quinolinol derivative for representative, can also use various metal complexs, anthracene derivant, double styrene benzene derivative, pyrene derivatives, oxazole derivative, poly-to vinylbenzene (Polyparaphenylenevinylene) derivative etc.In addition, can consist of luminescent layer with material of main part and dopant material, as material of main part, except above-mentioned luminescent material, can use thiazole derivative, benzimidizole derivatives, poly-diakyl fluorene derivatives etc.In addition, as dopant material, can use quinacridone, tonka bean camphor, rubrene, perylene and their derivative, 1-benzopyran derivatives, Rhodamine Derivatives, amino-benzene ethene (aminostyryl) derivative etc.They are film forming separately, also can be with film forming after other material mixing use as individual layer, can also for the stepped construction between the layer of independent film forming, mix between the layer of film forming stepped construction or separately film forming layer with mixes rear film forming layer stepped construction.
In addition, can also use the phosphorescent luminescent material as luminescent material.As phosphorescent twinkler, can use the phosphorescence twinkler of the metal complex of iridium, platinum etc.Can use Ir (ppy)
3Deng green phosphorescence twinkler, the phosphorescence twinkler that FIrpic, FIr6 etc. are blue, Btp
2The phosphorescence twinkler that Ir (acac) etc. are red etc., with regard to the material of main part of this moment, inject/material of main part of the property transmitted as the hole, can use 4,4 '-two (N-carbazyl) biphenyl (below, referred to as CBP), the carbazole derivative such as TCTA, mCP etc.As the material of main part of electron-transporting, can use two (triphenyl silyl) benzene (below, referred to as UGH2), 2,2 ', 2 ' '-(1,3, the 5-phenylene)-three (1-phenyl-1H-benzoglyoxaline) (below, referred to as TPBI) etc.
The doping of phosphorescent luminescent material is for the purpose of avoiding concentration quenching in the material of main part, preferably,, mixes by common evaporation in the scope of 1～30 quality % with respect to luminescent layer integral body.
Except vapour deposition method, these materials can pass through the known method such as method of spin coating, ink jet method and form film.
Hole blocking layer as organic EL device of the present invention, except the compound that uses substituted bipyridyl of the present invention and pyrido indole ring structure to be situated between to be formed by connecting by phenylene and bathocuproine (below, referred to as BCP) etc. beyond the metal complex of the quinolinol derivatives such as phenanthroline derivative, BAlq, can also use various rare-earth complex, oxazole derivatives, triazole derivative, pyrrolotriazine derivatives etc. to have the compound of hole barrier effect.These materials can double as the material of electron transfer layer.They are film forming separately, also can be with film forming after other material mixing use as individual layer, can also for the stepped construction between the layer of independent film forming, mix between the layer of film forming stepped construction or separately film forming layer with mixes rear film forming layer stepped construction.Except vapour deposition method, these materials can pass through the known method such as method of spin coating, ink jet method and form film.
As the electron transfer layer of organic EL device of the present invention, except the compound that uses substituted bipyridyl of the present invention and pyrido indole ring structure to be situated between to be formed by connecting by phenylene and with A1q
3, BAlq beyond the metal complex of quinolinol derivative of representative, can also use various metal complexs, triazole derivative, pyrrolotriazine derivatives, oxadiazole derivative, thiadiazoles derivative, carbodiimide derivative, quinoxaline derivatives, phenanthroline derivative, Silole (silole) derivative etc.They are film forming separately, also can be with film forming after other material mixing use as individual layer, can also for the stepped construction between the layer of independent film forming, mix between the layer of film forming stepped construction or separately film forming layer with mixes rear film forming layer stepped construction.Except vapour deposition method, these materials can pass through the known method such as method of spin coating, ink jet method and form film.
Electron injecting layer as organic EL device of the present invention, except using substituted bipyridyl of the present invention and pyrido indole ring structure to be situated between the compound that is formed by connecting by phenylene, can also use an alkali metal salts such as lithium fluoride, cesium fluoride, the alkaline earth salts such as magnesium fluoride, the metal oxides such as aluminum oxide etc., in the preferred selection of electron transfer layer and negative electrode, these materials can be omitted.
And then, in electron injecting layer or electron transfer layer, can use the further N of normally used material in this layer has been mixed the metals such as caesium and the material that obtains.
As the negative electrode of organic EL device of the present invention, the electrode materials that work function that can aluminium is such is low, magnesium silver alloys, magnesium indium alloy, the such lower alloy of work function of aluminum magnesium alloy are used as electrode materials.
Below, by embodiment embodiments of the present invention are described more specifically, but the present invention is not limited to following embodiment.
Embodiment 1
(8-[4-{6-(naphthalene-2-yl)-[2,2 '] dipyridyl-4-yl } phenyl]-5-phenyl-5H-pyrido [4,3-b] indoles (compound 2) synthetic)
In reaction vessel, add 2 '-acetonaphthone 16.1g, iodine 24.2g and pyridine 72ml, heat, 100 ℃ of lower stirrings 3 hours.Be cooled to room temperature, behind the interpolation 170ml water, carry out purifying by recrystallization.70 ℃ of lower drying under reduced pressure 12 hours, thereby obtain 1-{2-(naphthalene-2-yl)-2-oxoethyl } brown powder of pyridine iodide 31.3g (yield is 88%).
At first; in reaction vessel, add 4-bromo-phenyl aldehyde 15.4g, 2-acetylpyridine 10.1g, methyl alcohol 140ml; after being cooled to while stirring-5 ℃; drip 3% (wt/wt) NaOH methanol solution 140ml; further stirred 2 days; adding the 1-{2-(naphthalene-2-yl) obtain-2-oxoethyl in the solution of therefrom preparation } pyridine iodide 31.3g, ammonium acetate 80.3g, methyl alcohol 180ml heat, 55 ℃ of lower stirrings 2 days.After being cooled to room temperature, extract the crude product of separating out by filtering, wash with methyl alcohol.70 ℃ of lower drying under reduced pressure 12 hours, thereby obtain the grey powder of 4-(4-bromophenyl)-6-(naphthalene-2-yl)-[2,2 '] dipyridyl 14.3g (yield is 39%).
With the 4-(4-bromophenyl) that obtains-6-(naphthalene-2-yl)-[2,2 '] dipyridyl 3.6g, 8-bromo-5-phenyl-5H-pyrido [4,3-b] indoles 3.7g, tetrakis triphenylphosphine palladium (0) 0.3g, 2M wet chemical 12.5ml, toluene 30ml, ethanol 7ml be added in the reaction vessel that nitrogen replacement crosses, and carries out while stirring 3 hours reflux.After being cooled to room temperature, extract the crude product of separating out by filtering.Crude product is passed through column chromatography (carrier: NH silica gel, elutriant: toluene) carry out purifying, obtain 8-[4-{6-(naphthalene-2-yl)-[2,2 ']-bipyridyl-4-yl }-phenyl]-white powder of 5-phenyl-5H-pyrido [4,3-b] indoles (compound 2) 3.1g (yield is 61%).
For the gained white powder, use NMR to carry out Structural Identification.
1The H-NMR measurement result is shown in Fig. 1.
By
1H-NMR (CDCl
3) detect the signal of following 28 hydrogen.δ(ppm)＝9.48(1H)、8.75-8.80(3H)、8.69(1H)、8.56(1H)、8.51(1H)、8.41(1H)、8.22(1H)、8.00-8.05(4H)、7.88-7.95(4H)、7.81(1H)、7.67(2H)、7.52-7.62(6H)、7.38(1H)、7.33(1H)。
Embodiment 2
(8-[4-{6-(xenyl-4-yl)-[2,2 '] bipyridyl-4-yl }-phenyl]-5-phenyl-5H-pyrido [4,3-b] indoles (compound 8) synthetic)
Carry out similarly to Example 1, by the synthetic 6-(xenyl-4-yl) of 4-biphenyl list ethyl ketone-4-(4-bromophenyl)-[2,2 '] dipyridyl.With the 6-(xenyl-4-yl) that obtains-4-(4-bromophenyl)-[2,2 '] dipyridyl 3.7g, 8-bromo-5-phenyl-5H-pyrido [4,3-b] indoles 3.3g, tetrakis triphenylphosphine palladium (0) 0.3g, 2M wet chemical 12ml, toluene 30ml, ethanol 7ml be added in the reaction vessel that nitrogen replacement crosses, and carries out while stirring 3 hours reflux.After being cooled to room temperature, extract the crude product of separating out by filtering.Crude product is passed through column chromatography (carrier: NH silica gel, elutriant: toluene) carry out purifying, obtain 8-[4-{6-(xenyl-4-yl)-[2,2 ']-bipyridyl-4-yl }-phenyl]-white powder of 5-phenyl-5H-pyrido [4,3-b] indoles (compound 8) 1.7g (yield is 34%).
For the gained white powder, use NMR to carry out Structural Identification.
1The H-NMR measurement result is shown in Fig. 2.
By
1H-NMR (CDCl
3) detect the signal of following 30 hydrogen.δ(ppm)＝9.49(1H)、8.74(3H)、8.57(1H)、8.51(1H)、8.33(2H)、8.12(1H)、8.00(2H)、7.95-8.05(3H)、7.80(3H)、7.65-7.75(4H)、7.60(2H)、7.55(2H)、7.50(2H)、7.35-7.43(2H)、7.34(1H)。
Embodiment 3
For compound of the present invention, (Bruker AXS K.K. system, DSC3100S) obtains fusing point and second-order transition temperature by the highly sensitive differential scanning calorimeter.
The fusing point second-order transition temperature
255 ℃ 122 ℃ of the compounds of the embodiment of the invention 1
246 ℃ 128 ℃ of the compounds of the embodiment of the invention 2
Compound of the present invention has the second-order transition temperature more than 100 ℃.This filminess that represents compound of the present invention is stable.
Embodiment 4
Use compound of the present invention, at the vapor-deposited film of ito substrate preparation thickness 100nm, use atmosphere photoelectron spectrum device (Riken Keiki Co., Ltd. manufacturing, AC-3 type) to measure work function.
Work function
The compound 6.06eV of the embodiment of the invention 1
The compound 6.15eV of the embodiment of the invention 2
Like this, compound of the present invention has the darker value of work function of the 5.4eV that has than common hole mobile material such as NPD, TPD, has large hole barrier ability.
Embodiment 5
The following making of organic EL device: as shown in Figure 3, be pre-formed ITO electrode as transparent anode 2 at glass substrate 1, thereon successively evaporation hole injection layer 3, hole transmission layer 4, luminescent layer 5, hole blocking layer 6, electron transfer layer 7, electron injecting layer 8, negative electrode (aluminium electrode) 9.
Particularly, will be formed with the glass substrate 1 usefulness organic solvent washing of ITO film of thickness 150nm after, come washing surface by oxygen plasma treatment.Then, this glass substrate with the ITO electrode is installed in the vacuum evaporation plating machine, is decompressed to below the 0.001Pa.Then, according to the compound 102 of the mode that covers transparent anode 2 with evaporation rate 6nm/ minute evaporation following structural formula, form the hole injection layer 3 that thickness reaches 20nm.On this hole injection layer 3, with the compound 103 of evaporation rate 6nm/ minute evaporation following structural formula, form the hole transmission layer 4 that thickness reaches 40nm.On this hole transmission layer 4 take the evaporation rate ratio as compound 104: the compound 104 of the evaporation rate binary evaporation following structural formula of compound 105=5:95 and the compound 105 of following structural formula form the luminescent layer 5 that thickness reaches 30nm.On this luminescent layer 5, with the compound (compound 2) of the evaporation rate 6nm/ minute evaporation embodiment of the invention 1, form hole blocking layer that thickness reaches 30nm hold concurrently electron transfer layer 6 and 7.On this hole blocking layer is held concurrently electron transfer layer 6 and 7, with evaporation rate 0.6nm/ minute evaporation lithium fluoride, form the electron injecting layer 8 that thickness reaches 0.5nm.At last, AM aluminum metallization forms the negative electrode 9 that thickness reaches 150nm.To the organic EL device of made, in air, under the normal temperature, carry out characteristic measurement.
The measurement result of the characteristics of luminescence the when organic EL device that will make the compound (compound 2) that uses embodiments of the invention 1 applies volts DS is shown in table 1 in the lump.
Embodiment 6
As the hold concurrently material of electron transfer layer 6 and 7 of the hole blocking layer among the embodiment 5, the compound (compound 2) of the embodiment of the invention 1 is replaced with the compound (compound 8) of the embodiment of the invention 2, under the condition identical with embodiment 5, make organic EL device.To the organic EL device of made, in air, under the normal temperature, carry out characteristic measurement.
The measurement result of the characteristics of luminescence in the time of will applying volts DS to the organic EL device of made is shown in table 1 in the lump.
[comparative example 1]
In order to compare, the hold concurrently material of electron transfer layer 6 and 7 of hole blocking layer among the embodiment 5 as the compound 106 of the following structural formula of electron transfer layer 7 (is for example replaced with, with reference to patent documentation 4), under the condition identical with embodiment 5, make organic EL device.To the organic EL device of made, in air, under the normal temperature, carry out characteristic measurement.The measurement result of the characteristics of luminescence in the time of will applying volts DS to the organic EL device of made is shown in table 1 in the lump.
[table 1]
As shown in table 1 such, be 10mA/cm for current density
2The time driving voltage, use the comparative example 1 of the compound 106 of aforementioned structural formula to be 5.95V, be the low voltage of 5.24V and embodiment 5 is 4.33V, embodiment 6, and then current density is 10mA/cm
2The time brightness, luminous efficiency, electrical efficiency all significantly improve.
The result who measures luminous starting voltage is as follows.
Organic EL device compound light-emitting starting voltage [V]
Embodiment 5 compounds 2 2.7
Embodiment 6 compounds 8 2.9
Comparative example 1 compound 106 3.1
Its result as can be known, with respect to the comparative example 1 of the compound 106 that has used aforementioned structural formula, embodiment 5 and 6 luminous starting voltage present lower voltage.
Hence one can see that, and the device of compound 106 that is used as the aforementioned structural formula of common electron transport material with use is compared, and the luminous efficiency of organic EL device of the present invention and electrical efficiency are all excellent, and then can realize the remarkable reduction of practical driving voltage.
Utilizability on the industry
Substituted bipyridyl of the present invention and pyrido indole ring structure Jie are good by the Electron Injection Characteristics of the compound that phenylene is formed by connecting, the hole barrier ability is excellent, and filminess is stable, and therefore, this compound is excellent as the compound that is used for organic EL device.By using this compound to make organic EL device, high-level efficiency can be accessed, and driving voltage can be reduced, improve weather resistance.For example, can in household electric equipment for gasification and lighting use, launch to use.
Description of reference numerals
1 glass substrate
2 transparent anodes
3 hole injection layers
4 hole transmission layers
5 luminescent layers
6 hole blocking layers
7 electron transfer layers
8 electron injecting layers
9 negative electrodes
Claims (8)
1. compound shown in the following general formula (1), that substituted bipyridyl and pyrido indole ring structure are situated between and are formed by connecting by phenylene,
In the formula (1), Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms; Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17
2. substituted bipyridyl according to claim 1 and the pyrido indole ring structure compound that is situated between and is formed by connecting by phenylene, it is the compound shown in the following general formula (1 '),
In the formula (1 '), Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms; Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17
3. substituted bipyridyl according to claim 1 and the pyrido indole ring structure compound that is situated between and is formed by connecting by phenylene, it is the compound shown in the following general formula (1 "),
Formula (1 ") in, Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms; Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17
4. organic electroluminescence device, it has at least one deck organic layer of pair of electrodes and clamping therebetween, it is characterized in that, the compound that substituted bipyridyl shown in the following general formula (1) and pyrido indole ring structure Jie are formed by connecting by phenylene is used as the constituent material of at least one organic layer
In the formula (1), Ar
1, Ar
2Optional identical or different, expression replaces or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or unsubstituted condensed polycyclc aromatic base; R
1～R
17Optional identical or different, the straight chain shape of expression hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, carbonatoms 1～6 or alkyl, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocycle or replacement or the unsubstituted condensed polycyclc aromatic base of a chain; W, X, Y, Z represent carbon atom or nitrogen-atoms; Herein, only any one is nitrogen-atoms among W, X, Y, the Z, does not have expression hydrogen atom or substituent R on the nitrogen-atoms of this moment
14～R
17
5. organic electroluminescence device according to claim 4 is characterized in that, described organic layer is electron transfer layer, and the compound shown in the above-mentioned general formula (1) is used as at least one constituent material in this electron transfer layer.
6. organic electroluminescence device according to claim 4 is characterized in that, described organic layer is hole blocking layer, and the compound shown in the above-mentioned general formula (1) is used as at least one constituent material in this hole blocking layer.
7. organic electroluminescence device according to claim 4 is characterized in that, described organic layer is luminescent layer, and the compound shown in the above-mentioned general formula (1) is used as at least one constituent material in this luminescent layer.
8. organic electroluminescence device according to claim 4 is characterized in that, described organic layer is electron injecting layer, and the compound shown in the above-mentioned general formula (1) is used as at least one constituent material in this electron injecting layer.
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| PCT/JP2012/000206 WO2012098849A1 (en) | 2011-01-18 | 2012-01-16 | Compound having pyridoindole ring structure and substituted bipyridyl group, and organic electroluminescent element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718342A (en) * | 2020-07-10 | 2020-09-29 | 北京燕化集联光电技术有限公司 | Novel organic material and application thereof |
| CN111825671A (en) * | 2020-07-10 | 2020-10-27 | 北京燕化集联光电技术有限公司 | Compound containing carbazole ring and application thereof |
| CN111825697A (en) * | 2020-07-10 | 2020-10-27 | 北京燕化集联光电技术有限公司 | Carbazole ring-containing compound and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6231009B2 (en) * | 2012-10-22 | 2017-11-15 | コニカミノルタ株式会社 | Transparent electrode, electronic device, and organic electroluminescence element |
| US9837620B2 (en) * | 2013-09-09 | 2017-12-05 | Hodogaya Chemical Co., Ltd. | Benzopyridoindole derivative and organic electroluminescent element |
| CN111718341B (en) * | 2020-07-10 | 2021-08-17 | 北京燕化集联光电技术有限公司 | Compound containing pyridoindole structure and application thereof in organic electroluminescent device |
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| JP2006080271A (en) * | 2004-09-09 | 2006-03-23 | Konica Minolta Holdings Inc | Organic electroluminescence element, lighting system and display device |
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- 2012-01-16 CN CN2012800057761A patent/CN103328475A/en active Pending
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| JP2006080271A (en) * | 2004-09-09 | 2006-03-23 | Konica Minolta Holdings Inc | Organic electroluminescence element, lighting system and display device |
| CN101663300A (en) * | 2007-03-15 | 2010-03-03 | 保土谷化学工业株式会社 | Compound wherein substituted bipyridyl group is connected with pyridoindole ring structure through phenylene group, and organic electroluminescent device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718342A (en) * | 2020-07-10 | 2020-09-29 | 北京燕化集联光电技术有限公司 | Novel organic material and application thereof |
| CN111825671A (en) * | 2020-07-10 | 2020-10-27 | 北京燕化集联光电技术有限公司 | Compound containing carbazole ring and application thereof |
| CN111825697A (en) * | 2020-07-10 | 2020-10-27 | 北京燕化集联光电技术有限公司 | Carbazole ring-containing compound and application thereof |
| CN111718342B (en) * | 2020-07-10 | 2021-08-17 | 北京燕化集联光电技术有限公司 | Novel organic material and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2669284A4 (en) | 2014-06-11 |
| TW201245191A (en) | 2012-11-16 |
| EP2669284A1 (en) | 2013-12-04 |
| JP5955228B2 (en) | 2016-07-20 |
| EP2669284B1 (en) | 2016-03-30 |
| TWI542586B (en) | 2016-07-21 |
| US10541369B2 (en) | 2020-01-21 |
| WO2012098849A1 (en) | 2012-07-26 |
| KR20140014135A (en) | 2014-02-05 |
| JPWO2012098849A1 (en) | 2014-06-09 |
| US20130292663A1 (en) | 2013-11-07 |
| KR101966468B1 (en) | 2019-04-05 |
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